The present invention relates to polymerization catalyst activator compounds, to methods of making these activator compounds, to polymerization catalyst systems containing these activator compounds, and to polymerization processes utilizing the same. More particularly, the invention relates to activator complexes including at least two Group 13 metals comprising one or more halogenated aryl groups, the metals bound to the oxygen atoms of a diol.
Polymerization catalyst compounds are typically combined with an activator (or co-catalyst) to yield compositions having a vacant coordination site that will coordinate, insert, and polymerize olefins. Typically, methylaluminoxane (MAO) is utilized to activate metallocene catalysts. Alternative activators for metallocenes and other single-site polymerization catalysts have been discovered in recent years.
Group 13 based Lewis acids having three fluorinated aryl substituents are known to be capable of activating transition metal compounds into olefin polymerization catalysts. Trisperfluorophenylborane is demonstrated in EP 0 425 697 and EP 0 520 732 to be capable of abstracting a ligand for cyclopentadienyl derivatives of transition metals while providing a stabilizing, compatible noncoordinating anion. The noncoordinating anions are described to function as electronic stabilizing cocatalysts, or counterions, for cationic metallocene complexes which are active for olefin polymerization. The term noncoordinating anion as used herein applies both to truly noncoordinating anions and coordinating anions that are at most weakly coordinated to the cationic complex so as to be labile to replacement by olefinically or acetylenically unsaturated monomers at the insertion site.
The synthesis of Group 13-based compounds derived from trisperfluorophenylborane are described in EP 0 694 548. These Group 13-based compounds are said to be represented by the formula M1 (C6F5)3 (where Mi is a Group 13 metalloid such as aluminum or boron) and are prepared by reacting the trisperfluorophenylborane with dialkyl or trialkyl Group 13-based compounds at a molar ratio of xe2x80x9cbasically 1:1xe2x80x9d so as to avoid mixed products, those including the type represented by the formula Mi(C6F5)nR3xe2x88x92n, where n=1 or 2. Utility for the tris-aryl aluminum compounds in Ziegler-Natta olefin polymerization is suggested.
U.S. Pat. No. 6,147,174 discloses an olefin polymerization process utilizing activator compounds of the formula RnAl(ArHal)3xe2x88x92n, where ArHal represents a halogenated aryl group and R represents a monoanionic group other than a halogenated aryl group.
V. C. Williams et al. 121 J. AM. CHEM. SOC. 3244-3245 (1999) disclose the synthesis of diborane activators (bis-pentafluorophenyl)boryl groups tethered via organic linkers. The problem with some of these Group 13-based activators in polyolefin polymerization is low activity, among other problems. What is need is an improved Group 13-based activator and method of polymerizing olefins that can utilize these metalloid-type activators.
The present invention solves these and other problems by providing a catalyst system and a method of polymerizing olefins, the catalyst system comprising a catalyst compound and an activator compound, wherein the activator compound is represented in one aspect by: 
wherein each M1 is a Group 13 atom;
each R3, R3xe2x80x2, R3xe2x80x3, and R3xe2x80x2xe2x80x3 group is independently selected from: C1 to C30 alkyls, C1 to C30 heteroatom containing alkyls, C1 to C30 alkoxys, halogenated C1 to C30 alkoxys, C2 to C30 alkenyls, C6 to C60 aryls, C6 to C60 aryloxys, halogenated C6 to C60 aryloxys, and C6 to C60 halogenated aryls; with the proviso that at least one of R3, R3xe2x80x2, R3xe2x80x3, and R3xe2x80x2xe2x80x3 is a fluorinated C6 to C60 aryl group
R1 and R2 are independently selected from substituted or unsubstituted C1 to C100 hydrocarbylenes, aliphatic or aromatic;
R, when present, is a substituted or unsubstituted C30 hydrocarbylene aliphatic or aromatic group; wherein when R is absent, R1 and R2 are bound together; and
x is 0 or an integer from 1 to 100.